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Yakubenko, Artyom A. ; Tupikina, Elena Yu. ; Antonov, Alexander S.

The Role of Conjugation in the Halogen−Lithium Exchange Selectivity: Lithiation of 4,6,7,9‐Tetrabromo‐1,3‐dimethyl‐2,3‐dihydro‐1H‐perimidine

Yakubenko, Artyom A. , Tupikina, Elena Yu. und Antonov, Alexander S. (2023) The Role of Conjugation in the Halogen−Lithium Exchange Selectivity: Lithiation of 4,6,7,9‐Tetrabromo‐1,3‐dimethyl‐2,3‐dihydro‐1H‐perimidine. Chemistry – A European Journal.

Veröffentlichungsdatum dieses Volltextes: 26 Jul 2023 04:55
Artikel
DOI zum Zitieren dieses Dokuments: 10.5283/epub.54521


Zusammenfassung

The first case of successful suppression of the coordination of a lithium atom with a dialkylamino group by the effective conjugation of the latter with the aromatic core has been discovered. This effect controls regioselectivity of the bromine-lithium exchange in 4,6,7,9-tetrabromo-1,3-dimethyl-2,3-dihydro-1H-perimidine, which leads to products with the most effective conjugation. As a result, ...

The first case of successful suppression of the coordination of a lithium atom with a dialkylamino group by the effective conjugation of the latter with the aromatic core has been discovered. This effect controls regioselectivity of the bromine-lithium exchange in 4,6,7,9-tetrabromo-1,3-dimethyl-2,3-dihydro-1H-perimidine, which leads to products with the most effective conjugation. As a result, the product of this quadruple exchange demonstrates no tendency of the coordination of the NMe groups to neighboring lithium atoms despite the absence of steric restrictions. Experimental results are explained by means of quantum chemical calculations: geometry optimization, natural bond analysis and scans using the modredundant scheme.



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Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftChemistry – A European Journal
Verlag:WILEY-V C H VERLAG GMBH
Ort der Veröffentlichung:WEINHEIM
Datum1 Juni 2023
InstitutionenChemie und Pharmazie > Institut für Organische Chemie
Identifikationsnummer
WertTyp
10.1002/chem.202301439DOI
Stichwörter / Keywords; organolithiums; conjugation; coordination; regioselectivity; naphthalene
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenZum Teil
URN der UB Regensburgurn:nbn:de:bvb:355-epub-545215
Dokumenten-ID54521

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